CN105624747A - Copper/graphene composite multi-layer heat dissipation film - Google Patents
Copper/graphene composite multi-layer heat dissipation film Download PDFInfo
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- CN105624747A CN105624747A CN201511022980.6A CN201511022980A CN105624747A CN 105624747 A CN105624747 A CN 105624747A CN 201511022980 A CN201511022980 A CN 201511022980A CN 105624747 A CN105624747 A CN 105624747A
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- heat dissipation
- graphene oxide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 160
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 57
- 239000010949 copper Substances 0.000 title claims abstract description 57
- 230000017525 heat dissipation Effects 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000011159 matrix material Substances 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 238000001962 electrophoresis Methods 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- 229940001516 sodium nitrate Drugs 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 5
- 229940038773 trisodium citrate Drugs 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 238000009713 electroplating Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000005855 radiation Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 238000003490 calendering Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K7/00—Constructional details common to different types of electric apparatus
- H05K7/20—Modifications to facilitate cooling, ventilating, or heating
- H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
Abstract
The invention discloses a copper/ graphene composite multi-layer heat dissipation film and a preparation method thereof. The heat dissipation film is formed by alternately superposing a graphene layer and a copper layer. The preparation method mainly comprises the following steps: sequentially coating a graphene film and copper on a metal matrix; and finally, dissolving the metal matrix to obtain the self-supported copper/ graphene composite multi-layer heat dissipation film. The heat dissipation film prepared by the method is high in heat dissipation efficiency, and is convenient to use.
Description
Technical field
The invention belongs to heat sink material technical field, especially a kind of copper/Graphene composite multi-layer heat dissipation film and its preparation method.
Background technology
Along with the development of large-scale integrated circuit and encapsulation technology, electronic product also develops to direction thin, light, little, make electronic product surface temperature also in continuous rising, and components and parts also urgently need the environment ability reliability service of a relative low temperature, otherwise reducing the life-span of electronic component, therefore the heat radiation of electronic product becomes a very outstanding problem.
Existing market portioned product carries out heat conduction and heat radiation by metal species, especially copper and aluminium, although the thermal conductivity of copper is (398W/mK), but weight is big, the application limiting it such as oxidizable, and the thermal conductivity of aluminium not high (237W/mK), it is very difficult to meet currently available products to the demand of heat conduction and heat radiation. The heat radiation of electronic product has been had certain improvement by the heat dissipation film that the natural graphite material used at present and the graphite material of synthetic are made, but graphite radiating film is mainly by making the methods such as the method for directly calendering after graphite treatment and polymer charing, greying, its tensile strength of heat sink material that surface is graphite is not high, frangible and granule dust is many, be inconvenient to install and use.
Graphene (Graphene) a kind of forms, with sp2 hybridized orbital, the flat film that hexangle type is honeycomb lattice by carbon atom, only the two-dimensional material of a carbon atom thickness. Graphene is the thinnest in the world is the hardest nano material also, thermal conductivity up to 5300W/m K, higher than carbon nanotube and diamond so that grapheme material becomes the nova got most of the attention in heat sink material field. But the heat-conducting effect of Graphene exists anisotropy, only the radiating effect on two dimensional planes is better for it, and heat conductivility in the vertical but sharply gives a discount, and existing Graphene heat dissipation film does not all address this problem. In addition, Graphene heat dissipation film prepared by existing technique is one layer of heat radiation structure, and heat radiation efficiency need further raising.
Summary of the invention
The present invention is intended to solve existing heat dissipation film and there is the shortcomings such as heat radiation efficiency is low, heat dissipation direction is limited, and provides a kind of copper/Graphene composite multi-layer heat dissipation film and its preparation method.
In order to achieve the above object, present invention employs following technical scheme.
A kind of copper/Graphene composite multi-layer heat dissipation film, is alternately formed by stacking primarily of graphene layer, layers of copper.
Further, described copper layer thickness is 0.1��1 ��m, and the thickness of described graphene layer is 0.1��1 ��m.
Further, the top layer of described copper/Graphene composite multi-layer heat dissipation film is graphene layer, and middle layer is that layers of copper and graphene layer are alternately formed by stacking, and its total thickness is 10��50 ��m.
A preparation method for copper/Graphene composite multi-layer heat dissipation film, mainly comprises the following steps: step one, gets piece of metal matrix, electrochemical deoiling; Step 2, deposits one layer of graphene oxide film on metallic matrix; Then utilize electrochemical process that the graphene oxide film in step 2 is reduced to graphene film; Step 3, the metallic matrix that surface is covered with graphene film puts into the plating liquid of copper ions, at graphene film electroplating surface one layer of copper; Step 4, successively repeating step two, step 3, thus formed by the copper/Graphene multilayered structure of graphene layer, layers of copper alternately superposition at metal base surface, cleaning is dried; Step 5, uses acid fluid dissolves metallic matrix, cleans and dries, obtains the copper/Graphene composite multi-layer heat dissipation film of self-supporting.
As the technical scheme that the present invention improves, described metallic matrix is any one in aluminium, zinc, iron.
As the technical scheme that the present invention improves, the effect of described electrochemical deoiling is the greasy dirt removing metal base surface so that it is surface possesses wetting ability, its processing parameter is oil removing powder 10��20g/L, sodium hydroxide 2��5g/L, temperature 40��50 DEG C, ultrasonic cleaning time 2��10min.
As the technical scheme that the present invention improves, first described step 2 adopts Hummer ' s method to prepare graphene oxide for (1), then graphene oxide is dissolved in deionized water, add the Sodium dodecylbenzene sulfonate that massfraction is 0.1%��1%, ultrasonic disperse 2��5h, is mixed with the graphene oxide solution of 0.5��3mg/mL; (2) described graphene oxide solution is put into electrolyzer, metallic matrix after processing taking step one is as positive pole, Pt sheet is negative pole, the spacing of two electrodes is located at 1��5cm, the voltage of 1��5V is applied at electrode two ends, reaction 5min��5h, makes graphene oxide electrophoresis to covering metal matrix surface, and taking-up is dried; (3) metallic matrix by surface band graphene oxide obtained in step (2) puts into the PBS that pH value is 7��9, it it is still positive pole taking metallic matrix, Pt sheet is negative pole, electrode potential is regulated to be at-2��-3V, reaction 5min��0.5h, make the graphene oxide of metal base surface be reduced into Graphene, then take out to clean and dry.
Preferably, first described step 2 adopts Hummer ' s method to prepare graphene oxide for (1), is then dissolved in deionized water by graphene oxide, adds the Sodium dodecylbenzene sulfonate that massfraction is 0.5%, ultrasonic disperse 3h, is mixed with the graphene oxide solution of 2mg/mL; (2) described graphene oxide solution is put into electrolyzer, metallic matrix after processing taking step one is as positive pole, Pt sheet is negative pole, the spacing of two electrodes is located at 3cm, the voltage of 3V is applied at electrode two ends, reaction 0.5h, makes graphene oxide electrophoresis to the metal base surface being coated with nickel, and taking-up is dried; (3) metallic matrix by surface band graphene oxide obtained in step (2) puts into the PBS that pH value is 8, it it is still positive pole taking metallic matrix, Pt sheet is negative pole, electrode potential is regulated to be at-2.3V, reaction 10min, making the graphene oxide of metal base surface be reduced into Graphene, then take out to clean and dry, obtained Graphene thickness is 0.35 ��m.
As the technical scheme that the present invention improves, first described step 2 adopts Hummer ' s method to prepare graphene oxide for (1), then graphene oxide is dissolved in deionized water, add the Sodium dodecylbenzene sulfonate that massfraction is 0.1%��1%, ultrasonic disperse 2��5h, is mixed with the graphene oxide solution of 0.5��3mg/mL; (2) the described graphene oxide solution getting every square centimeter of 0.1��1mL is dripped and is overlayed on metallic matrix, dries; (3) metallic matrix by surface band graphene oxide obtained in step (2) puts into the PBS that pH value is 7��9, take metallic matrix as positive pole, Pt sheet is negative pole, electrode potential is regulated to be at-2��-3V, reaction 5min��0.5h, make the graphene oxide of metal base surface be reduced into Graphene, then take out to clean and dry.
Preferably, first described step 2 adopts Hummer ' s method to prepare graphene oxide for (1), is then dissolved in deionized water by graphene oxide, adds the Sodium dodecylbenzene sulfonate that massfraction is 0.5%, ultrasonic disperse 3h, is mixed with the graphene oxide solution of 2mg/mL; (2) the described graphene oxide solution getting every square centimeter of 0.5mL is dripped and is overlayed on the part that metallic matrix is coated with nickel, dries; (3) metallic matrix by surface band graphene oxide obtained in step (2) puts into the PBS that pH value is 8, take metallic matrix as positive pole, Pt sheet is negative pole, electrode potential is regulated to be at-2.3V, reaction 20min, making the graphene oxide of metal base surface be reduced into Graphene, then take out to clean and dry, obtained Graphene thickness is 0.67 ��m.
As the technical scheme that the present invention improves, described step 3 is that the metallic matrix that surface is covered with graphene film is put into primarily of the electroplate liquid that copper sulfate 20��50g/L, trisodium citrate 25��50g/L, SODIUMNITRATE 4��8g/L, sodium hydroxide 20��40g/L, ethylene glycol 50��150g/L, excess water are formed, control current density 5��10A/dm2, pH value 7��9, temperature 30��50 DEG C processing condition under electroplate 10min��0.5h.
Preferably, described step 3 is that the metallic matrix that surface is covered with graphene film is put into primarily of the electroplate liquid that copper sulfate 40g/L, trisodium citrate 40g/L, SODIUMNITRATE 6g/L, sodium hydroxide 30g/L, ethylene glycol 100g/L, excess water are formed, control current density 8A/dm2, pH value 8, temperature 45 DEG C processing condition under electroplate 20min, obtained copper layer thickness is 0.89 ��m.
As the technical scheme that the present invention improves, described step 5 is the dilute hydrochloric acid acid fluid dissolves metallic matrix with 5��10%.
Preferably, the mass percent of described dilute hydrochloric acid is 8%.
Useful effect
The copper of the present invention/Graphene composite multi-layer heat dissipation film utilizes copper particle to drive in each layer graphene by the heat energy of bottom Graphene, then two dimensional plane radiating modes of each layer graphene are utilized to fall apart by heat energy fast so that the heat radiation efficiency of existing Graphene heat dissipation film significantly improves. In addition, namely Graphene and copper particle carry out when chemically reactive is stronger replacing galvanic deposit, exist to intersect and infiltrate mutually between Graphene and copper particle, and the connection between the graphene layer of thus the present invention and layers of copper is very tight.
Accompanying drawing explanation
Fig. 1 is the structural representation of the copper/Graphene composite multi-layer heat dissipation film of the present invention.
Embodiment
Now by reference to the accompanying drawings the specific embodiment of the present invention is described in detail.
The copper of the present invention/Graphene composite multi-layer heat dissipation film, is alternately formed by stacking primarily of graphene layer 1, layers of copper 2. Wherein, the number of plies of described graphene layer and layers of copper can set according to the requirement of electronics big area industrial application, in the present invention, the top layer of described copper/Graphene composite multi-layer heat dissipation film is preferably graphene layer, middle layer is that layers of copper and graphene layer are alternately formed by stacking, and its total thickness is 10��50 ��m.
The preparation method of the copper of the present invention/Graphene composite multi-layer heat dissipation film, mainly comprises the following steps: step one, gets piece of metal matrix, electrochemical deoiling; Step 2, deposits one layer of graphene oxide film on metallic matrix; Then utilize electrochemical process that the graphene oxide film in step 2 is reduced to graphene film; Step 3, the metallic matrix that surface is covered with graphene film puts into the plating liquid of copper ions, at graphene film electroplating surface one layer of copper; Step 4, successively repeating step two, step 3, thus formed by the copper/Graphene multilayered structure of graphene layer, layers of copper alternately superposition at metal base surface, cleaning is dried; Step 5, uses acid fluid dissolves metallic matrix, cleans and dries, obtains the copper/Graphene composite multi-layer heat dissipation film of self-supporting. The metal that described metallic matrix answers Selection radio copper easily molten, such as aluminium, zinc, iron.
In step one, the effect of described electrochemical deoiling is the greasy dirt removing metal base surface so that it is surface possesses wetting ability, and its processing parameter is oil removing powder 10��20g/L, sodium hydroxide 2��5g/L, temperature 40��50 DEG C, the ultrasonic cleaning time 2��10min.
First described step 2 adopts Hummer ' s method to prepare graphene oxide for (1), then graphene oxide is dissolved in deionized water, add the Sodium dodecylbenzene sulfonate that massfraction is 0.1%��1%, ultrasonic disperse 2��5h, it is mixed with the graphene oxide solution of 0.5��3mg/mL; (2) described graphene oxide solution is put into electrolyzer, metallic matrix after processing taking step one is as positive pole, Pt sheet is negative pole, the spacing of two electrodes is located at 1��5cm, the voltage of 1��5V is applied at electrode two ends, reaction 5min��5h, makes graphene oxide electrophoresis to covering metal matrix surface, and taking-up is dried; (3) metallic matrix by surface band graphene oxide obtained in step (2) puts into the PBS that pH value is 7��9, it it is still positive pole taking metallic matrix, Pt sheet is negative pole, electrode potential is regulated to be at-2��-3V, reaction 5min��0.5h, make the graphene oxide of metal base surface be reduced into Graphene, then take out to clean and dry. Preferably, first described step 2 adopts Hummer ' s method to prepare graphene oxide for (1), is then dissolved in deionized water by graphene oxide, adds the Sodium dodecylbenzene sulfonate that massfraction is 0.5%, ultrasonic disperse 3h, is mixed with the graphene oxide solution of 2mg/mL; (2) described graphene oxide solution is put into electrolyzer, metallic matrix after processing taking step one is as positive pole, Pt sheet is negative pole, the spacing of two electrodes is located at 3cm, the voltage of 3V is applied at electrode two ends, reaction 0.5h, makes graphene oxide electrophoresis to the metal base surface being coated with nickel, and taking-up is dried; (3) metallic matrix by surface band graphene oxide obtained in step (2) puts into the PBS that pH value is 8, it it is still positive pole taking metallic matrix, Pt sheet is negative pole, electrode potential is regulated to be at-2.3V, reaction 10min, making the graphene oxide of metal base surface be reduced into Graphene, then take out to clean and dry, obtained Graphene thickness is 0.35 ��m.
As another embodiment of the present invention, first described step 2 adopts Hummer ' s method to prepare graphene oxide for (1), then graphene oxide is dissolved in deionized water, add the Sodium dodecylbenzene sulfonate that massfraction is 0.1%��1%, ultrasonic disperse 2��5h, is mixed with the graphene oxide solution of 0.5��3mg/mL; (2) the described graphene oxide solution getting every square centimeter of 0.1��1mL is dripped and is overlayed on metallic matrix, dries; (3) metallic matrix by surface band graphene oxide obtained in step (2) puts into the PBS that pH value is 7��9, take metallic matrix as positive pole, Pt sheet is negative pole, electrode potential is regulated to be at-2��-3V, reaction 5min��0.5h, make the graphene oxide of metal base surface be reduced into Graphene, then take out to clean and dry. Preferably, first described step 2 adopts Hummer ' s method to prepare graphene oxide for (1), is then dissolved in deionized water by graphene oxide, adds the Sodium dodecylbenzene sulfonate that massfraction is 0.5%, ultrasonic disperse 3h, is mixed with the graphene oxide solution of 2mg/mL; (2) the described graphene oxide solution getting every square centimeter of 0.5mL is dripped and is overlayed on the part that metallic matrix is coated with nickel, dries; (3) metallic matrix by surface band graphene oxide obtained in step (2) puts into the PBS that pH value is 8, take metallic matrix as positive pole, Pt sheet is negative pole, electrode potential is regulated to be at-2.3V, reaction 20min, making the graphene oxide of metal base surface be reduced into Graphene, then take out to clean and dry, obtained Graphene thickness is 0.67 ��m.
Described step 3 is that the metallic matrix that surface is covered with graphene film is put into primarily of the electroplate liquid that copper sulfate 20��50g/L, trisodium citrate 25��50g/L, SODIUMNITRATE 4��8g/L, sodium hydroxide 20��40g/L, ethylene glycol 50��150g/L, excess water are formed, control current density 5��10A/dm2, pH value 7��9, temperature 30��50 DEG C processing condition under electroplate 10min��0.5h. Preferably, described step 3 is that the metallic matrix that surface is covered with graphene film is put into primarily of the electroplate liquid that copper sulfate 40g/L, trisodium citrate 40g/L, SODIUMNITRATE 6g/L, sodium hydroxide 30g/L, ethylene glycol 100g/L, excess water are formed, control current density 8A/dm2, pH value 8, temperature 45 DEG C processing condition under electroplate 20min, obtained copper layer thickness is 0.89 ��m.
Described step 5 is the dilute hydrochloric acid acid fluid dissolves metallic matrix with 5��10%. Preferably, the mass percent of described dilute hydrochloric acid is 8%.
The announcement of book and instruction according to the above description, above-mentioned enforcement mode can also be carried out suitable change and amendment by those skilled in the art in the invention. Therefore, it is intended that the invention not be limited to embodiment disclosed and described above, some modifications and changes of the present invention also should be fallen in the protection domain of claim of the present invention. In addition, although employing some specific terms in this specification sheets, but these terms are just for convenience of description, and the present invention does not form any restriction.
Claims (10)
1. copper/Graphene composite multi-layer heat dissipation film, is alternately formed by stacking primarily of graphene layer, layers of copper.
2. copper according to claim 1/Graphene composite multi-layer heat dissipation film, it is characterised in that: described copper layer thickness is 0.1��1 ��m, and the thickness of described graphene layer is 0.1��1 ��m.
3. copper according to claim 2/Graphene composite multi-layer heat dissipation film, it is characterised in that: the top layer of described copper/Graphene composite multi-layer heat dissipation film is graphene layer, and middle layer is that layers of copper and graphene layer are alternately formed by stacking, and its total thickness is 10��50 ��m.
4. a preparation method for copper/Graphene composite multi-layer heat dissipation film, mainly comprises the following steps: step one, gets piece of metal matrix, electrochemical deoiling; Step 2, deposits one layer of graphene oxide film on metallic matrix; Then utilize electrochemical process that the graphene oxide film in step 2 is reduced to graphene film; Step 3, the metallic matrix that surface is covered with graphene film puts into the plating liquid of copper ions, at graphene film electroplating surface one layer of copper; Step 4, successively repeating step two, step 3, thus formed by the copper/Graphene multilayered structure of graphene layer, layers of copper alternately superposition at metal base surface, cleaning is dried; Step 5, uses acid fluid dissolves metallic matrix, cleans and dries, obtains the copper/Graphene composite multi-layer heat dissipation film of self-supporting.
5. the preparation method of copper according to claim 4/Graphene composite multi-layer heat dissipation film, it is characterised in that: described metallic matrix is any one in aluminium, zinc, iron.
6. the preparation method of copper according to claim 4/Graphene composite multi-layer heat dissipation film, it is characterized in that: the effect of described electrochemical deoiling is the greasy dirt removing metal base surface, its surface is made to possess wetting ability, its processing parameter is oil removing powder 10��20g/L, sodium hydroxide 2��5g/L, temperature 40��50 DEG C, the ultrasonic cleaning time 2��10min.
7. the preparation method of copper according to claim 4/Graphene composite multi-layer heat dissipation film, it is characterized in that: first described step 2 adopts Hummer ' s method to prepare graphene oxide for (1), then graphene oxide is dissolved in deionized water, add the Sodium dodecylbenzene sulfonate that massfraction is 0.1%��1%, ultrasonic disperse 2��5h, is mixed with the graphene oxide solution of 0.5��3mg/mL; (2) described graphene oxide solution is put into electrolyzer, metallic matrix after processing taking step one is as positive pole, Pt sheet is negative pole, the spacing of two electrodes is located at 1��5cm, the voltage of 1��5V is applied at electrode two ends, reaction 5min��5h, makes graphene oxide electrophoresis to covering metal matrix surface, and taking-up is dried; (3) metallic matrix by surface band graphene oxide obtained in step (2) puts into the PBS that pH value is 7��9, it it is still positive pole taking metallic matrix, Pt sheet is negative pole, electrode potential is regulated to be at-2��-3V, reaction 5min��0.5h, make the graphene oxide of metal base surface be reduced into Graphene, then take out to clean and dry.
8. the preparation method of copper according to claim 4/Graphene composite multi-layer heat dissipation film, it is characterized in that: first described step 2 adopts Hummer ' s method to prepare graphene oxide for (1), then graphene oxide is dissolved in deionized water, add the Sodium dodecylbenzene sulfonate that massfraction is 0.1%��1%, ultrasonic disperse 2��5h, is mixed with the graphene oxide solution of 0.5��3mg/mL; (2) the described graphene oxide solution getting every square centimeter of 0.1��1mL is dripped and is overlayed on metallic matrix, dries; (3) metallic matrix by surface band graphene oxide obtained in step (2) puts into the PBS that pH value is 7��9, take metallic matrix as positive pole, Pt sheet is negative pole, electrode potential is regulated to be at-2��-3V, reaction 5min��0.5h, make the graphene oxide of metal base surface be reduced into Graphene, then take out to clean and dry.
9. the preparation method of copper according to claim 4/Graphene composite multi-layer heat dissipation film, it is characterized in that: described step 3 is that the metallic matrix that surface is covered with graphene film is put into primarily of the electroplate liquid that copper sulfate 20��50g/L, trisodium citrate 25��50g/L, SODIUMNITRATE 4��8g/L, sodium hydroxide 20��40g/L, ethylene glycol 50��150g/L, excess water are formed, control current density 5��10A/dm2, pH value 7��9, temperature 30��50 DEG C processing condition under electroplate 10min��0.5h.
10. the preparation method of copper according to claim 4/Graphene composite multi-layer heat dissipation film, it is characterised in that: described step 5 is the dilute hydrochloric acid acid fluid dissolves metallic matrix with 5��10%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061504A (en) * | 2009-11-13 | 2011-05-18 | 中国科学院兰州化学物理研究所 | Method for synthesizing graphene-containing composite thin film material |
| CN102548353A (en) * | 2010-12-31 | 2012-07-04 | 上海杰远环保科技有限公司 | Stack-up type membrane heat dissipation structure and realization method thereof |
| CN102555324A (en) * | 2010-12-31 | 2012-07-11 | 上海杰远环保科技有限公司 | High-radiation film type metal compound material and manufacturing method thereof |
| KR20140003218A (en) * | 2012-06-29 | 2014-01-09 | 세종대학교산학협력단 | Method for forming stacked graphene, stacked graphene thereof, and devices including the same |
| CN103625029A (en) * | 2013-11-25 | 2014-03-12 | 许子寒 | Graphene heat-conducting device |
-
2015
- 2015-12-29 CN CN201511022980.6A patent/CN105624747B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061504A (en) * | 2009-11-13 | 2011-05-18 | 中国科学院兰州化学物理研究所 | Method for synthesizing graphene-containing composite thin film material |
| CN102548353A (en) * | 2010-12-31 | 2012-07-04 | 上海杰远环保科技有限公司 | Stack-up type membrane heat dissipation structure and realization method thereof |
| CN102555324A (en) * | 2010-12-31 | 2012-07-11 | 上海杰远环保科技有限公司 | High-radiation film type metal compound material and manufacturing method thereof |
| KR20140003218A (en) * | 2012-06-29 | 2014-01-09 | 세종대학교산학협력단 | Method for forming stacked graphene, stacked graphene thereof, and devices including the same |
| CN103625029A (en) * | 2013-11-25 | 2014-03-12 | 许子寒 | Graphene heat-conducting device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| GB2562805B (en) * | 2017-05-26 | 2022-02-23 | Graphitene Ltd | Heat spreader and method of manufacture thereof |
| CN107579201A (en) * | 2017-09-14 | 2018-01-12 | 珠海格力电器股份有限公司 | A kind of polylayer forest and preparation method thereof |
| CN107579201B (en) * | 2017-09-14 | 2023-07-18 | 珠海格力电器股份有限公司 | Multilayer body and preparation method thereof |
| CN107815720A (en) * | 2017-09-15 | 2018-03-20 | 广东工业大学 | A kind of self-supporting redox graphene coating and its preparation method and application |
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| CN112490204A (en) * | 2020-11-26 | 2021-03-12 | 西安交通大学 | Graphene-based sandwich structure heat dissipation film, semiconductor device and preparation method of semiconductor device |
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